Nu, nu&#39;-bis-(thiazolyl)-phenylenediamines



3,299,087 N,N-BIS-(THIAZOLYL)-PHENYLENEDIAMINES John D.. Spivack, Spring Valley, and Martin Dexter,

White Plains, N.Y., assignors to Geigy Chemical Corporation, Ardsley, N.Y., a corporation of Delaware No Drawing. ()riginal application Apr. 24, 1961, Ser. No. 104,805. Divided and this application Aug. 6,

1965, Ser. No. 487,348

3 Claims. (Cl. 260-3063) This application is a continuation-in-part of Serial No. 28,839, filed May 13,1960, and now abandoned.

This invention relates to novel substituted thiazole compounds. In one aspect thereof, the invention comprises a first class of new substituted thiazole compounds of the formula:

wherein R represents alkyl having greater than 3 carbon atoms, preferably from 4 to 18 carbon atoms, e.g. butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, hendecyl, dodecyl, pentadecyl, octadecyl, etc., substituted aryl, preferably alkylphenyl, especially alkylphenyl having from 7 to 24 carbon atoms, e.g. tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, hendecylphenyl, dodecylphenyl, pentadecylphenyl, octadecylphenyl, etc.;

R represents hydrogen;

R and R when taken jointly, represent--CH CH CH CH and X represents aryl, preferably naphthyl, substituted aryl,

preferably substituted phenyl, especially hydroxyphenyl, aminophenyl, alkanamidophenyl, e.g. acetamidophenyl, propionamidophenyl, caproamidophenyl, lauramidophenyl, stearamidophenyl, alkylhydroxyphenyl, e.g. methylhydroxyphenyl, ethylhydroxyphenyl, propylhydroxyphenyl, butylhydroxyphenyl, pentylhydroxyphenyl, hexylhydroxyphenyl, nonylhydroxyphenyl, dodecylhydroxyphenyl, octadecylhydroxyphenyl, etc., lower alkoxyphenyl, lower alkylaminophenyl, phenylaminophenyl, aminobiphenyl, aceuaphthyl, and substituted thiazolyl of the formula:

wherein R is as above defined.

A second class of new substituted thiazoles comprises compounds for the formula:

wherein R represents alkyl, such as e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, decyl, hendecyl, dodecyl, octadecyl, etc., and aryl, preferably phenyl; R represents alkyl, preferably lower alkyl, e.g. methyl,

ethyl, propyl, butyl, pentyl, and hexyl, aryl, preferably phenyl, and substituted aryl, preferably substituted i United- States Patent "ice phenyl, and alkanoyl, e.g. formoyl, acetyl, propionyl, butyryl, etc., caproyl, lauroyl and stearoyl, etc.; and

Y represents substituted aryl, e.g. substituted phenyl,

preferably hydroxyphenyl.

A third class of new substituted thiazoles comprises compounds of the formula:

N--C-R X-NH-ii ii-Ru S (III) wherein R represents hydrogen and alkyl having from 1 to 3 carbon atoms, e.g. methyl, ethyl, propyl;

R represents alkyl, e.g. methyl, ethyl, propyl, butyl,

pentyl, heXyl, octyl, dodecyl, octadecyl, etc.; and

X represents substituted aryl, preferably hydroxyphenyl. A fourth class of new substituted thiazoles comprises compounds of the formula:

A fifth class of new substituted thiazoles comprises compounds of the formula:

wherein R represents methyl, ethyl, propyl; and

X represents aminophenyl and alkylhydroxyphenyl, e.g.

methylhydroxyphenyl, ethylhydroxyphenyl, propylhydroxyphenyl, butylhydroxyphenyl, octylhclroxyphenyl, dodecylhydroxyphenyl, octadecylhydroxyphenyl, etc. A sixth class of new substituted thiazoles comprises compounds of the formula:

wherein R represents hydroxy, amino, alkylamino, preferably lower alkylamino, alkyl, e.g. methyl, ethyl, propyl, butyl, octyl, dodeeyl, octadecyl, etc., alkanamido, e.g. forrnarnido, acetamido, propionamido, butyramido, caproamido, lauramido, stearamido, etc.;

R represents hydrogen, and, when R represents alkyl, then R represents hydroxy.

In this specification the term lower alkyl signifies an alkyl group having from 1 to 6 carbon atoms, and the expression -tsignifies -tertiary-.

The novel substituted 2-aminothiazole compounds disclosed hereinabove are useful as chemical intermediates, e.g. in the synthesis of sulfathiazoles. Additionally, some of the substituted Z-aminothiazoles of the invention are useful in muscle relaxant compositions. Also, the novel Z-aminothiazoles hereinabove described are useful stabilizers for various unstable materials.

Up to the present time, the use of the foregoing classes of substituted thiazoles in stabilizing organic material, e.g. polypropylene, has not been known. It has now surprisingly been found that many organic materials are stabilized against deterioration, e.g. oxidative and/ or light induced and/or thermal deterioration, by incorporating therein a stabilized quantity of a substituted thiazole according to the present invention.

The substituted thiazoles of the invention are thus also particularly useful in stabilizing lubricating oils of various types, including aliphatic esters, polyalkylene oxides,.

silicones, esters of phosphoric and. silicic acids, highly fluorine-substituted hydrocarbons, etc.

The substituted thiazoles of the present invention are also useful in stabilizing fatty materials, including oils of animal and vegetable origin which tend to deteriorate, e.g. on standing and exposure to atmospheric oxygen; also saturated and unsaturated hydrocarbons which tend to deteriorate on storage, such as e.g. gasolines, both natural and synthetic, in particular, saturated and unsaturated gasolines, etc.; jet fuel, diesel oil, mineral oil, fuel oil, drying oil, waxes, resins, etc.

A particularly effective stabilizer of the invention is 2,2'-imino-bis-4-(p-t-butylphenyl)-thiazole which is especially useful in stabilizing polyolefinic materials, e.g. polypropylene. Another especially valuable stabilizer is 2- (p-aminoanilino)-4-t-butylthiazole which is an effective stabilizer for relatively unstable organic material, e.g. waxes, particularly paraflin wax, hydrocarbon oil of mineral origin, in particular, mineral oil; gasoline, both natural and synthetic; oil of animal origin, in particular, lard; oils of vegetable origin, in particular, cotton seed oil. Still another valuable stabilizer is Z-(m-aminoanilino)-4-t-butylthiazole which is especially effective in stabilizing polymeric material, e.g. polyethylene and aldehydes, such as heptaldehyde. other preferred stabilizers are 2-(m-hydroxyanilino)- and 2-(p-hydroxyanilino)-4-tbutylthiazole which are particularly useful in stabilizing elastomers, both natural and synthetic, e.g. polyisoprene rubber.

The choice of .a specific substituted thiazole for stabilization of a given unstable material will depend upon several factors. Availability and cost of raw materials for the manufacture of the stabilizer and effective inhibitory action of the stabilizer, including duration and degree of activity, are among the factors which control the choice of a specific stabilizer for a specific substrate which is normally subject to oxidative deterioration. Toxicity, color, stability to light and solubility are also important factors.

In general, the stabilizers of the invention are employed in a concentration of from about 0.001% to about 5% by weight, preferably from about 0.01% to about 1% by weight, based on the total weight of the stabilized material. The specific concentration used varies with the substrate and the stabilizer, but the following generalizations can be made.

Concentrations of about 0.001% to about 0.1% by weight of the antioxidant in polyethylene are useful. In polypropylene, from about 0.05% to about 1% by weight of the stabilizer are used. For polystyrene, from about 0.1% to about 1% by weight is useful. In rubber, concentrations of from about 0.05% to about 1% are useful. In mineral oils, concentrations of from about 0.005% to about 1% by weight of stabilizer are used. Gasolines are stabilized with from about 0.01% to about 0.1% by Weight of stabilizer, preferably 0.05% by weight. Fatty material of animal origin, such as lard, is stabilized ,Withfrom about 0.001% to about 0.1% by weight of stabilizer. Oils of vegetable origin, such as cotton seed oil, are stabilized with from about 0.001% to about 0.1% by weight of stabilizer.

Hydrocarbon material, such as cycloolefins, e.g. cyclohexene, is advantageously stabilized with from about 0.001% to about 1% by weight of the stabilizers of the present invention. The same concentrations of stabilizer are used to stabilize aldehydes, such as e.g. about 0.01% by weight of stabilizer in heptaldehyde. High temperature lubricants which are essential diesters, e.g. diisoamyladipate, are stabilized with from about 0.5% to about 5%, preferably about 2% by weight of a stabilizer according to the invention.

The compounds of this invention may also be used to stabilize organic material in combination with other additive agents, such as e.g. antioxidants, pourpoint depressants, corrosion and rust inhibitors, dispersing agents,

. demulsifiers, antifoaming agents, carbon black, accelerators and other chemicals used in rubber compounding, plasticizers, color stabilizers, heat stabilizers, UV absorbers, dyes and pigments, etc.

The thiazoles of the invention which are useful as stabilizers are prepared advantageously by the reaction of arylthioureas with halocarbonyl compounds, as in reaction (1) below. Alternatively, an arylamine is reacted with a Z-aminothiazole to produce a Z-arylaminothiazole according to reaction (2) below. Still further, an arylamine can be reacted with a 2-halothiazole according to reaction (3) below.

A fourth alternate synthesis includes the following reaction:

In the foregoing reaction schemes, X stands for halogen; Ar represents aryl; and R and R are any suitable group in accordance with the desired compounds according to the present invention.

The sources of the u-halocarbonyl compounds of reaction (1) are illustrated below in Table I.

The aromatic thioureas which are used to prepare some of the compounds of the invention are made by known procedures involving the reaction of aromatic amines with either sodium, potassium or ammonium thiocyanates in acidic media:

wherein Ar is an aromatic nucleus which may be substituted or unsubstituted, and M is the sodium, potassium or ammonium ion. A substantial number of these thioureas have been previously characterized in the literature, e.g. as shown in Table'II, whereas Table III illustrates some intermediates not previously character- 'ized in the literature.

i ABLE ,L-a-HALOOARBONYL GOMPOUNDQUSED AS INTERMEDIATES IN THE INVENTION Compound Structure Reference or Source 1 1-br0mo'3,3-dlmethylcHmc-c-cm-Br J. B. Dickey et 81., 1'.

butanone-2. Org. Chem. 20, 499-500 ll 1-br0motrldecanone-2 CH1(CH2)10C-CH9BI Lutz et al., J. Org.

Chem., 12, 767' (1047).

S-Bromoheptaldehyde CH3(CHI)4CHCHO Yanovskaya at 111., J.

1 Gen. Chem. (USSR) Br 22, 1598-1602 (1952),

(0.11. 1953, 9257). ii 4,4-dlmethyl-3- (CHOIC CH CH1 Fierens, Bull. Soc.

chloropentanOHB-Z. Chlm. Belg. 64, 772

p-t-Butyl-phenacyl ol-oni-c OQ-t-Oni. Ritter and Sokol, .T.

chloride. Am. Chem. Soc. 70,

3419-21 (1948). p-n-Dodecylphenacyl CICHaC OQ-n-CuHn Using method of Auers chloride. Ber. 39, 3757 (1906) who prepared p-ethylphenacyl chloride.

TABLE II.-N-ARYL SUBSTITUTED THIOUREA COM- POUNDS USED AS INTERMEDIATES IN THE INVENTION Aryl substiment MP Literature Reference Aryl Substituent Literature Reference (CzHshN-G- 132-133 A. B. Wang, Scientia $111108. (Peking) 3, 301-4 (1954), NH, 167-168 Masai) Shlmot'aul, J. Pharm. 1956 8496a) Soc. Japan 72, 328-30 (1952), (0.11. 1953 16271), d).

TABLE III.AROMATIC THIOUREAS USED As INTER- 40 MEDIATES IN THE INVENTION 190 Masao Shimotanl, Lee. 01:. Compound: Melting point, C. 1-(Z-hydroxy-S-t-octylphenyl)-2-thiourea 160-161 1-(p-aminobiphenyl)-2-thiourea 270 1,1'-p,p-biphenylene-bis-2-th iourea 270 H, l-(p-anilinophenyl)-2-thiourea 198 l i 1-phenyl-l,1'-p-phenylene-bis-Z-thiourea 218 B.RArventlevl et Bk, A0231. l-(p-acetamidophenyl)-2-thiourea 204-205 e 0 u are oma Fil la la l, Studii Carma l-(m-acetarmdophenyl)-2-tl 10urea 194-195 stunt-1N0. 1-2, 234-43 1-(p-lauram1d0phenyl)-2-tl11ourea 196-208 1953), 0.14. 1956,15894). l-(p-ste'aramidophenyl)-2-thiourea M 202-206 l-(p-aminophenyl)-1-rnethyl-2-thiourea 177-178 The methods of preparing the compounds of the invention will be more clearly understood from the examples which illustrate the invention, but are not meant to limit the same thereto. In the examples, temperatures are in degrees centigrade and parts are by Weight, unless otherwise noted. The relationship of parts by weight to parts by volume is as that of grams to cubic centimeters.

2-ARYLAMINO-4-ARYLTHIAZOLES OH 161 Masao Shimotani, Lee. 011:.

214 Masao Shimotani, Lee Cit.

Example 1.2-(0-methoxyanilino) -4-phenylthiaz0le Phenacyl chloride (15.4 parts) is dissolved in 50 parts by volume of benzene and added to a dispersion of 18.2

parts of o-methoxyphenylthiourea in 150 parts by volume of ethanol. The reaction mixture is heated at reflux $11 176 Beyerman and Bontekoe, Re.

. 130481 s Bhatld and 13, (about 75) for several hours. The reaction mixture is gi gh gg g fi y then diluted with 300 parts of water and neutralized with saturated aqueous sodium bicarbonate solution and the product is extracted with ether. After drying the other Tray. chlm. 72, 643-52 (1953), (C.A. 1954 9966a).

solution over anhydrous sodium sulfate, the product is isolated, removing the ether by distillation. The residue sakurell Chem soc, from ether is recrystallized from isopropanol yielding J ,Id.Ch .Set3, gga 92 3 5 22 parts of 2 o methoxyanillno 4 phenylthlazole (M.P. 3258b). -86

Ryohel Oda and Ryoichi Examples 2-10.2-substituted amino-4-phenylthiazoles In an analogous manner to Example 1, the following products were made:

Example 12.--2- (p-acetamidophenylamino)-4-phenylthiazole Phenacyl chloride (7.7 parts) is dissolved in 35 parts by volume of benzene and added at room temperature 5 with stirring to a dispersion of p-acetamidophenylthiourea (10.5 parts) in methyl Cellosolve (100 parts by volume). The reaction mixture is then heated at about 80 (25) for 4 hours, then cooled and filtered. The solid Subst. Phenylthiourea Em Phenacyl- Product, M.P., Crystalliza- N chloride, parts by wt. 0. tion Solvent X R Parts parts by wt.

by wt.

2 H 16 8 15 4 19.0 179-180 Benzene.

3 H 16. 7 15 4 12. 0 163-165 Isopropanol.

4 H 16.7 15 4 15.0 133-135 Benzene.

14.0 123-125 Ethylene chloride.

15.0 160-162 Isopropanol.

Example 11.2-p-hydr0xyanilin0-4-phenylthiazole 2-p-hydroxyanilino-4-phenylthiazole (5 parts), melting 70 at 203 upon recrystallization from isopropanol, is obtained by reacting 22 parts of p-aminophenol with 15 parts of 2-amino-4-phenylthiazole hydroiodide in 250 parts by volume of ethylene glycol at 185 under nitrogen.

obtained (15.3 parts, 88%) is recrystallized once from ethanol, having a melting point of 255-257". The hydrochloride, so obtained, is then suspended in 100 parts by volume of ethanol and brought to pH 8 with saturated aqueous sodium bicarbonate, stirred for one hour, filtered and washed with water. The 2-(p-aceta-midophenylamino)-4-phenylthiazole is recrystallized repeatedly from isopropanol until a constant melting point of 75 179-180 is reached.

9. Example 13.-2-(m-acetamidoplzenylamino)-4-phenylthiazole This compound is made substantially as described in Example .12 for the p-acetamido analog. The residue from ether weighs 18.5 parts. Recrystallization from a mixtureof ethylene chloride and benzene yields Z-(macetamidophenylamino)-4-phenylthiazole, melting at 145- 146.

Example 14.-2-(p-lauramidophenylamino)-4-phenylthiazole This compound is made substantially as described in Example 12 for the p-acetamido analog, by reacting 17.5 parts of l-(p-lauramidophenyl)-2-thiourea with 7.7 parts of phenacyl chloride. After neutralization with aqueous sodium bicarbonate, the product is extracted with chloroform. The 2-(p-lauramidophenylamino)-4'phenylthiazole is isolated by distillation of the solvent. After recrystallization from benzene, the Z-(p-Iauramidophenylamino)-4-phenylthiazole melts at ISO-151.

Example 15.2- (p-lauramidophenylamino) -4-p-t-butylphenylthiazole This compound is made substantially as described in Example 14 for 2-(p-lauramidophenylamino)4-phenylthiazole by reacting 17.5 parts of l-(p-lauramidophenyD- Z-thiourea with 10.5 parts of p-t-butylphenacyl chloride. The 2-(p-lauramidophenylamino)-4-p-t-butylphenyl thiazole, thus obtained (17.3 parts) melts at 16 3.5-164.5 after recrystallization from benzene.

Example 16.-2- (p-stearamidophenylamino -4-phenylthiazole This compound is made substantially as described in Example 12 for the p-acetamido analog, by reacting 15 parts of 1-(p-stearamidophenyl)-2-thiourea with 5.3 parts of phenacyl chloride. The 2-(p-stearamidophenylamino)- 4 phenylthiazo1e isisolated by filteringand drying the precipitate obtained on neutralization with aqueous sodium bicarbonate. After recrystallization from chloroform, the Z-(p-stearamidophenylamino)-4-phenylthiazole (12.6 parts) melts at 146-1475.

Example 1 7 .2- (N Jauioy l-2-hydr0xy-5 -t-0cty lphenylamino) -4-phenylflziaz0le 3.1 parts of lauroyl chloride, dissolved in 15 parts by volume of dioxane, are added dropwise at 28 during 10 minutesto a solution of 5.5 parts of the compound described in Example 9 and 1.1 parts of pyridine dissolved in parts by volume of dioxane. The reaction mixture is heated at 35 to for 1 hour and then poured into 300 parts of water. The dispersion is extracted with ether and dried over anhydrous sodium sulfate. The residue, after distillation of the ether (7 parts), is crystallized successively from 75 parts by volume of hexane, containing 5 parts of benzene, from carbon tetrachloride, and from hexane. The 2-(N-lauroyl-2- hydroxy-S-t-dctylphenylamino)-4-phenylthiazole, thus obtained, melts at 106.5- 108.

If, in Example 17, acetyl chloride (1.09 parts) is substituted for lauroyl chloride, then 2-(N-acetyl-2-hydroxy- 5-t-octylphenylamino)-4-phenylthiazole is obtained.

If, in Example 17, stearoyl chloride (4.23 parts) is substituted for lauroyl chloride, then 2-(N-stearoyl-2-hydroxy-5-t-octy1phenylamino)-4-phenylthiazole is obtained.

Example 18.2- (p-acetamidophenylamino -4-(p-tbutylplzenyl)-thiaz0le This compound is made using p-t-butylphenacyl chloride, described by Ritter et al., J. Am. Chem. Soc. 70 3419 (1948), the other reagents being the same as described in Example 12. The reaction is run under the same conditions as above (4 hours 80i5). Filtration yields 16.5 parts (90%) of solid. In this case the free amine is obtained directly. Recrystallization from aqueous ethanol yields 2-(p-acetamidophenylarnino)-4-(p-t- 1O but ylphenyl)-thiazole, having a melting point of 198- 200.

Example 19.2-(m-acetamid0phenylamino)-4-(p-t-butylphenyl)-thiaz0le This compound is made substantially as described in Example 18 for the p-acetamido analog. The residue from a mixture of ethylene chloride and benzene yields a product melting at 139-140".

Example 20'.2- u-naphthylamino -4- (p-t-butylplzenyl) thiazole p-t-Butylphenacyl chloride (11 parts) is dissolved in 35 parts by volume of benzene and added to a dispersion of 10 parts of u naphthylthiourea in 150 parts by volume of ethanol over a period of 20 minutes at 50?. 'Ihe reaction mixture is then heated at reflux (about 75) for 3 hours, diluted with about 500 parts of Water, then made alkaline with 100 parts by volume of 10% aqueous sodium hy droxide and finally extracted first with ether and then with benzene. The combined extracts are dried over anhydrous sodium sulfate. The residue, obtained by distillatiori of the solvent at reduced pressure (10 parts), is recrystallized from benzene. 2-(a-Naphthylamino)-4-(p-tbutylphenyl)-thiazole is obtained as white crystals melting at 214-215".

Example 21 .2-(p-diethylaminoanilino)-4(p-t-butylphenyl)-thiaz0le to give 18 parts of 2-(p-diethylaminoanilino)-4-(p-t-butylphenyl)-thiazole, melting at 230. The product is crystallized from benzene and melts at 231-233 as slightly ofi-white crystals.

Example 22.--2-[ p-anilino)-phenylamino]-4-(p-tbutylphenyl) -thiazole p-t-Butylphenacyl chloride (10.5 parts) is dissolved in 25 parts by volume of benzene and added dropwise at 28 over a period of 10 minutes to a dispersion of p-(ani1ino)- phenylthiourea in 77 parts by volume of methyl Cellosolve. The reaction mixture is heated at 80 for 3 /2 hours, cooled and diluted with parts by volume of 5% aqueous sodium bicarbonate, the precipitated product being extracted with ether. The ether extract is washed with water, dried over sodium sulfate, the ether being removed by distillation at about 15 mm. Hg pressure. The 2-[(p-anilino)-phenylamino] 4 (p-t-butylphenyl)-thiazole (19 parts), crystallized from isopropanol, melts at l62--163.

Example 23.-2-(p-amino-N-mezhylanilino)-4-(p-tbutylphenyl)-thiaz0le To a solution of 7.83 parts of 1-(p-aminophenyl)-1- methyl-2-thiourea in 100 parts by volume of methyl Cellosolve at 70-75 is added a solution of 9.1 parts of p-tbutylphenacyl chloride in 35 parts by volume of benzene over 15 minutes. The reaction is essentially complete after 3.5 hours at 70-75 After cooling, the reaction is neutralized with aqueous sodium bicarbonate and the product is isolated by extraction with ether. The residue (15.9 parts), after removal of the ether, is recrystallized successively from a solvent mixture of benzene and hexane, and thereafter from ethanol. The 2-(p-amino-N- methylanilino)-4-(p-t-butylphenyl)-thiazole, so obtained, has a melting point of 161l62.

If, in Example 23, 1-(p-arninophenyl)-l-hexyl-2-thiourea (15.1 parts) is substituted for l-(p-aminophenyl-l- Example 24.--2-[4-(p-aminophenyl) -phenylamino] -4- (p-t-butylphenyl) -thiazle p-t-Butylphenacyl chloride (4.2 parts) is dissolved in 21 parts by volume of benzene and added dropwise over a period of 10 minutes at 28 to a dispersion of 4-(p-arninophenyl)-phenylthiourea (6 parts) in 72 parts of methyl Cellosolve. The dispersion is heated for 6 hours at80, then diluted with 100 parts by volume of aqueous sodium bicarbonate and extracted with ether. The product, after removal of ether at 15 mm. Hg pressure, weighs 7 parts and is crystallized successively from benzene, a mixture of isopropanol-benzene, and benzene once again. The 2-[4-(p-aminophenyl)-phenylamino]-4 (p-t-butylphenyl)-thiazole, so obtained, melts at 187-188.

Example 25 .2- p-aminoanilino) -4- p-n-dodecylphenyl thiazole p-n-Dodecylphenacyl chloride (8.1 parts), obtained according to Auer [Ber. 39 3757-64 1906)] using n-dodecylbenzene, is dissolved in 25 parts by volume of henzene and added to a dispersion of 4.2 parts of p-aminophenylthiourea in 100 parts by volume of ethanol. The reaction mixture is heated at reflux (75) over a period of 2 hours in a nitrogen atmosphere. The reaction mixture is neutralized with base, extracted with ether, the ether extract being washed with water and then dried over urea (10.5 parts) is substituted for p-aminophenylthio- 12 anhydrous sodium sulfate. The residue, obtained after distillation of the ether (10 parts), is recrystallized from isopropanol. The 2-(p-arninoanilino) 4-(p-n-dodecylphenyl)-thiazole, thus obtained, melts at 121.

If, in Example 25, 3-t-butyl-4-hydroxyphenylthiourea (5.3 parts) is substituted for p-aminophenylthiourea, then 2-(3-t-butyl-4-hydroxyphenyl) 4 (p-n-dodecylphenyl)- thiazole is obtained.

If, in Example 25, 3-n-dodecyl-4 hydroxyphenylthiourea (8.4 parts) is substituted for p-aminophenylthiourea, then 2-(3-n-dodecyl-4-hydroxyphenyl)-4 (p-n-dodecylphenyl)-thiazole is obtained.

If, in Example 25, 3-n-octadecyl-4-hydroxyphenylthiourea, then 2- 3-n-octadecyl-4-hydroxyphenyl) -4- (p-n-dodeoylphenyD-thiazole isohtained.

' If, in Example 25, p-n-octadecylphenacyl chloride (10.2 parts) is substituted for p-n-dodecylphenacyl chloride, then 2- (p-arninoanilino -4- (p-n-octadecylphenyl) -thiazole is obtained.

Examples 2630.-Substituted 2-amino-4-p-ndodecyphenylthiazoles In analogous manner to Example 25 the following compounds were prepared:

Subst. Phenylthiourea S P" I] Dodeoyl- Product Crystallization EX. No. X-NR-C-NH2 phenacyl- Yield, M.P., C. Solvent chloride, parts by wt. parts by wt. X R Parts by wt.

26 H 5 8. 1 9. 0 Isopropanol.

27 H 4. 2 8. 1 10. 0 136-137 Benzene.

28 H 4. 5 8.1 11. 5 106 Benzenehexane.

29 H 5 8.1 3 122-124 Isopropanol.

30 H 7. 29 9. 6 2. 9 -175 Isopropanol chloroform.

13 Z-ACENAPHTHYLAMINO SUBSTITUTED THIAZOLES Example 31 .2-( 5 -acenaphthylamino) -4-( p-tbutylphenyl)-thiazole pyridine. The reaction temperature during addition rises to a maximum of 32, whereupon the reaction mixture is heated at reflux (about 75) for two hours. The reaction mixture is diluted with about 200 parts of water and extracted with ether, the ether extract being Washed with water and aqueous sodium bicarbonate and dried over anhydrous sodium sulfate. The product (10 parts), obtained by distillation of the solvent, is dissolved in hexane and filtered free of a minor amount of hexane-insoluble material. The hexane filtrate is treated twice with activated carbon and the 2,2-imino-bis-(4-hendecylthiazole) crystallizes on cooling, melting at 79-80. After recrystallization from isopropanol, the 2,2'-imino-bis(4-hendecylthiazole) melts at 80-81 aqueous dispersion isneutralized with aqueous ammonium hydroxide to pH 9 to 10 and extracted several times with I benzene, the combined extracts being Washed with water Examples 3435-212 'Iml'w'bls'(4'subsnmted thlazoles) and then dried over anhydrous sodium sulfate; the sodium sulfate is filtered off and thefiltrate is distilled. During R-O-N the removal of benzene by distillation at about 15 mm. L Hg .pressure, the 2-(5-acenaphthylamino)-4-(p-t-butylphenyl)-thiazole separates (14 parts), melting at '196 s 2 198. On recrystallization from a solvent mixture of henzeneand hexane, the 2-(5-acenaphthylamino)-4-(p-t-butyl- The following compounds were prepared in a manner phenyl)-thiazole melts at 198-200. analogous to Example 32:

Product yield Ex. 2,4-dithio- Parts Crystallization N 0. biuret, parts a-Haloketone by wt. solvent by wt. R Parts M.P.

by wt. C

34 6.7 a-Bromopinacol' 17.9 (CH3)3C 13 114- Ethanol water.

one. 115

35 3.5 p-n-Dodecylphen- 16.2 11.5 104- Isopropanol.

acyl chloride. 105

l Il-O12 25 2,2-IMINO-BIS( l-SUBSTITUTED THIAZOLES) Example 32.2,2-imin0-bis-4-(p-t-butylphenyl) -thiazole tained on distillation of the ether (26 parts), is recrystallized from a solvent mixture of benzene and isopropanol. The 2,2-imino-bis-4-(p-t-butylphenyl)-thiazole, so obtained, melts at 25 6-257".

If, in Example 32, p-n-octadecylphenacyl chloride (40.6 parts) is substituted for p-t-butylphenacyl chloride, then 2,2 imino-bis-4-(p-n-octadecylphenyl)-thiazole is obtained.

Example 33.-2,2'-imin0-bis-(4-hendecyllhiaz0le) a-B-romotridecanone (11.1 parts), dissolved in 35 parts by volume of benzene, is added over a period of 15 minutes at 28. to a dispersion of dithiobiuret (2.7 parts) in 100 parts by volume of ethanol containing 3.2 parts of 2-ARYLAMINO-4-ALKYL THIAZOLES Exam pl 3 6 .2- p amin'oanilino -4-methy ltlziazole Chloropropanone (7 parts) is dissolved in 25 parts by volume of benzene and added to a dispersion of 12 parts of p-aminophenylthiourea in 150 parts by volume of ethanol. The reaction mixture is heated at reflux (about 75) for several hours. The reaction mixture is then neutralized with saturated sodium bicarbonate solution, and the product is extracted with ether. After drying the ether solution over anhydrous sodium sulfate, the product is isolated by removing the ether by distillation. The residue from ether weighs 7 parts and is recrystallized from benzene. The Z-p-aminoanilino-4-methylthiazole, so obtained, melts at l4l.

If, in the foregoing Example 36, 1-chloroctanone-2 (6.5 parts) is substituted for chloropropanone, then 2-(paminoanilino)-4-hexylthiazole is obtained.

Examples 37-40.-Substituted 2-amin0-4-methylthiaz0les The following compounds were prepared in an analogous manner to Example 36:

Subst. Phenylthiourea Ex. N0. l-Ohloro- Product M.P., O. Crystallization propanone, Yield, parts Solvent [I parts by wt. by wt. X-C-NHz X R Parts by 37 H 18.0 10.0 4. 0 147-148 Isopropano.

38 H 16. 7 9. 2 Liquid (analysis)*.

NHz

OH 39 Q H 11.0 3.6 11. 0 158160 Cyclohexane.

t-CsHn 40 (011;) 0- 0 (CH H 5.0 1.7 4.0 174-175 Benzenehexane.

* See the following table:

Calculated 58. 53% 5. 38% 20. 48% Found 58. 32% 5. 70% 20. 24%

Example 41.--2- (p-aminoanilino) -4-t-butylthiaz0le 1-Brom0-3,3-dimethylbutanone-2 (9.0 parts), whose preparation is described by J. B. Dickey et aL, J. Org. Chem. 20, 499-500 (1955), is dissolved in 25 parts by volume of benzene and is added to a dispersion of paminophenylthiourea (9.0 parts) in 75 parts by volume of ethanol at about 50 over a period of about 10 minutes. The reaction mixture is heated at reflux for 3 hours, neutralized with base and extracted with ether, the ether extract being dried over anhydrous sodium sulfate. The residue obtained after distillation of the ether weighs 16.9 parts and is recrystallized from benzene. The Z-(p-aminoanilino)-4-t-butylthiazole, thus isolated, melts at 145- 146.

If, in the foregoing Example 41, l-chlorodecanone-Z (9.5 parts) is substituted for 1-brom0-3,3-dimethylbutanone-Z, then 2-(p-aminoanilino)-4-octylthiazole is obtained.

Examples 4252.Substiluted 2-amino-4-t-butylthiazoles The following compounds were prepared in a manner 75 parts by volume of ethanol at 49-50 over a period analogous to Example 41: of to minutes. The reaction mixture is heated at Subst. Phenylthiourea l-Bromo- 3,3-dimethyl- Product Crystalliza- Ex. No. X-NR-C-NHz butanone-2, Yield, M.P., 0. tion Solvent parts by wt. parts by wt.

X R Parts by wt.

42 H 9.0 9.0 12.4 145-145.5 Benzene.

43.. H 9L0" 9.0 14.5 178-179' Benzene.

44 H 9. 2 9. 0 11.5 Liq.

45 H 9.0 9.0 11.0 117-119 Hexanebenzene.

OH O

46" H 16.8 17.9 17.5 149-151 Benzene.

| 47 I-I 10. 0 8. 9 13. 0 89-90 Petrol. etherhexane.

48 H 14.0 8.9 18.5 128-129 Benzene hexane.

t-CaH 49 H 1- 5. 0 3. 2 5. 0 113-114 Petrol. ether.

(CH3)3C- C(CH3)| I OH 50 12.2 8.9 16.0 161-1625 Vl'aterisopropanol.

51 N H; H 9.0 9.0 11.8 134-135 Benzene.

52 H 16.7 17.9 15.0 101-102 Carbon tetrachloride.

NH:Z

Example 53.--2-(o-hydroxyphenylamino)-4-n-hendecylreflux for 3 hours and neutralized with parts thiazole by volume of an aqueous solution containing 5 parts of l-bromotridecanone-Z (6.9 parts), whose preparation sodium bicarbonate. The reaction mixture is extracted is described by Lutz et al., J. Org. Chem. 12, 767 (1947), with ether, the extract being dried over anhydrous sodium is dissolved in 25 parts by volume of benzene and is added sulfate. The residue, obtained after distillation of the to a dispersion of o-hydroxypheuylthiourea (4.5 parts) in 75 ether, weighs 10.5 parts and is crystallized from isopro- 19 panol. 2-o-hydroxyphenylamino-4-n-hendecylthiazole, so obtained, melts at 122-123.

Examples 545 9.Sub.s1tituted 2-amino-4-hendecylsolution is neutralized with aqueous sodium bicarbonate. The precipitated base is extracted with ether, the ether extract being dried over anhydrous sodium sulfate. The sodium sulfate is filtered off and the ether removed by thiazales 5 distillation. The residue is recrystallized from a solution fi of benzene and hexane, yielding pure 2-p-hydroxyanilino- OH S-n-pentylthiazole, melting at 105-106".

s Example 61 .2-0-hydroxya1nilino-5-n-pentylthiazole The following Compounds were P p in a 1113111161 u-Bromoheptaldehyde (9.65 parts), as prepared and deanalogous to Example 53: scribed by Yanovskaya et al., J. Gen. Chem. (USSR) 22,

Subst. Phenylthiourea E 1-B -t P (1 NE. X-NR-PJNH2 dec i fi ei iel df M.P., C. z ii li parts by wt. parts by wt. Solvent X R Parts by Wt.

54 H 4.5 6.9 7.5 93-94 Hexane.

55 H 4.5 6.9 6.2 70-71 Carbon tetrachloride. NH@

56 H 4.5 6.9 8.0 8586 Hexane.

57 H 4.5 6.9 9.0 47-4s.5 Hexane.

as H 4.5 6.9 9.0 58-60 Petrol. ether.

I 59 (I) H 2.9 4.0 5.4 68-60 Isopropanol.

Z-ARYLAMINO-S-ALKYL THIAZOLES 1598-1602 (1952), CA. 47, 9257 (1953), is dissolved in Example 60.2-p-hydroxyanilin0-5-n-pentylthiazole 55 zsoparts by of hermetic added .dmpvYiSe at 25* 30 over a period of minutes to a dispersion of 8.4 q -Br m h p y P as Prepared and parts of o hydroxyphenylthiourea in 75 parts by volume Scrlbed by Yanovskaya 6t Chem; U of ethanol. The mixture is heated at reflux in a nitrogen 1958-1602 (1952), CA. 47, 9257 (1953), Is diss lv d 111 atmosphere for 2 hours. The reaction solution is then P y of benlfille and added P Y at diluted with 150 parts by volume of water containing 5 Over a Perlod of 10 nflnutes f dlsperslon of parts of sodium bicarbonate and thoroughly extracted in 3 Parts of P' y YI In 75 P y Yolume portions of 80 parts by volume of ether. The combined of ethanol- The mlxtlll'e heated refluK 111 a f f ether extracts are Washed with 150 parts by volume of atmosphere for 2 hours. The yellow reaction solution i water, the ether layer being dried over anhydrous sodium dlluwd Wlth 91 PY Volume of Water contalmng sulfate. The residue, obtained after distillation of ether f' lit tg i gi s gig $6 232??? 32 il g fii gg g (13.7 parts), is recrystallized from hexane-benzene, yieldether. The combined ether extracts are washed with 150 2g; ggg; entylthlazole of a melting parts by volume of Water and dried over anhydrous sodium p If E 61 m M h sulfate. The residue, obtained after the distillation of Xamp e oroproplona e yde Parts) the ether (10 parts), is dissolved in ethanol, treated with wbstltuted for aibmmqhePtalfkhyde, then gaseous hydrogen chloride while cooling, whereupon 7.5 amhnP's'methylthlazole as Obtalnedparts of the hydrochloride of If m Example 61, a-chlorotetradecanal (12.3 parts) is pentylthiazole crystallize. This hydrochloride melts at Substltuted for f p i y then Y Y- 152-154. 7 parts of the hydrochloride are dispersed in ani1in05-d0decylthiazole 1s obtalned. Water with sufiicient ethanol to give a clear solution. The If, in Example 61, a-chloroeicosanal (16.5 parts) is sub- 21 stituted for a-bromoheptaldehyde, then 2 o hydroxyanilino-5-o-octadecylthiazole is obtained.

Example 62.-2-o-hydroxyanilin0-4-methyl-S-tthe benzene solution is added dropwise at 35 to a dispersion of p-phenylenedithiourea (9.0 parts) in 100 parts by volume of methyl Cellosolve over a period of 20 minl-bromo 3,3 dimethylbutanone-Z (15.0 parts) as described by J. B. Dickey et al., J. Org. Chem. 20, 499-500 utes. After the addition, the reaction mixture becomes butylthmzole 5 homogeneous and is heated at reflux for 4 /2 hours in a fh ly P P as nitrogen atmosphere. The reaction solution is then poured $Crlbed y Flerens, Bull- Chlmg- 772 1955 into 150 parts by volume of water containing 4 parts of dissfillved in 25 Parts y y of benlene a added sodium hydroxide, and is extracted with 4 portions of 60 dfOpWlse at 25-300 a dlsperslon of y y-p y parts by volume of ether. The combined ether extracts are thiOUFea P 111 75 Parts y Volume of ethanol T11e Washed with 200 parts by volume of water, and filtered to reactlon mixture is heated at IefluX under Illirogefl remove a small amount of insoluble precipitate. The clear 9 2 P The Clear Yellow 5 sollltlon 1S ether solution is dried over anhydrous sodium sulfate and dllllted Wlth 150 Parts of Water contamlng 5 Palrts of the desired product (14 parts) is isolated by recovery of dium bicarbonate and extracted with 3 portions of 70 parts h id upon di ill i of the ether Th by volume of ether. The ether extract is dried over an- 15 pheny1ene-'bi -(2-arnin0-4-t-butylthiaz0le) is purified by hydrous sodium sulfate. The ether is then distilled Off a successive crystallization from 1,2-dichlorethane and benthe residue (3.0 parts) is recrystallized from 1:1 isozene nd has a melting point of 199-202". Holland-Petroleum ether, Yielding unfeacted Y Y- In a fashion similar to Example 63, other N,N'-p-phenylphenylthiourea. The residue fro mthe filtrate 1s recrystal- -bi (zi .4- b it d hi i are d as fol. lized from n-hexane, yielding pure 2-o-hydroxyanilino-4- lo methyl-5-Fb1ltY1thiaZ01e, melting at If, in Example 63, l-chlorotetradecanone-Z (19.7 parts) If, in Example 62, 2,2-dimethyl-3-c lOr e- (7- is substituted for 1-bron1o-3,3-dimethylbutanone-2, then parts) is substitutedfo-r 4,4-dimethyl-3-chloropentanone-2, N,N'- h 1 bi (2- i 4-d d i hi i i bthen 2-o-hydroxyanilino-4-hexyl-5-t-butylthiazole is obtained, 1 tained. If, in Example 63, l-chloroeicosanone-Z (26.4 parts) is ill Example 2,2-di1'1mth31'3#2111010tilde(ilnone-4 substituted for 1-bromo-3,3-dimethylbutanone-2, then N,

parts) is SllbStltlltCd for 4,4-d1methyl-3-chloropenta- N' p phenylene-bis-(2-amino 4. octadecylthiazole) is obnone-2, then 2-o-hydroxyanilino-4-dodecyl-5-t-butylthiami d, Z016 is obtained. E l 4 7 If, in Example 62, (2,2-dimethyl-1-chloropropyl)-octxamp es adecylketone (12.8 parts) is substituted for 4,4-dimethyl- I11 llke f i 129 to 15143111171963, 3-chloropentanone-2, then 2-0-hydroXyanilino-4-octadecy1- Phenylene bis ammo 4 Substltuted 3113120165) S-t-butylthiazole is obtained. were made as follows:

Product Subst. Phenylthiourea Rl ("3 W h ("P411 [1 a-Haloketone, H-C C-NR NIB-C CH Ex. N0. XN RCNH1 parts by wt. S s

X R Parts Ri Parts by wt. Ml C. Crystallization by wt. Solvent i 64 NCN1I H 11.3 010111000113, CH3 5 227-229 Methanol 9.2. isopropanol. R

65 H 5.5 C15C0HzCOCHa, CH9, 1.3 167-168 Isopropanol.

s I l| R 66 H 11.3 CICHzCOCuHs, GuHs 15 135-136 Carbon tetra- S 15.4. chloride. NR J-NH2 i 67 NR-CNH1 H 24 C13(1)HzCOCuH5, CsHs 31 228-229 Isopropanol.

N,N'-PHENYLENE-BIS-( 2-AMINO-4-SUBSTITUTED Example 68 .N,N '-p-ph eny lene-bis- (2-amino-4- THIAZOLES) 70 p-t-butylplzenylthiazole) Example 63.N,N-p phenylene-bis-(2-amino-4-tbutylthiazole) p-t-Butylphenacyl chloride (21 parts) is dissolved in 45 parts by volume of benzene and added to a dispersion of 11.5 parts of p-phenylene-dithiourea in 100 parts by (1955), is dissolved in 25 parts by volume of benzene and volume of ethanol over a period of 20 minutes at 50.

The reaction mixture is heated at reflux (74) for 3 hours and then diluted with 100 parts by volume of water. The reaction mixture is made alkaline with about 150 parts by volume of 10% aqueous sodium hydroxide and extracted with ether. The ether is then distilled OE and the crude residue Washed with methanol; it melts at 250. The N,N p phenylene bis (2 amino 4 p t butylphenylthiazole), so obtained, is recrystallized from ethylene chloride, giving white crystals melting at 253-255.

Example 69.N,N'-bis-(4-p-t-butylphenyl-2- thiazolyl) -N-phenyl-p-phenylenediamine p-t-Butylphenacyl chloride (19.0 parts) is dissolved in 50 parts by volume of benzene and added dropwise to a Examples 71-73 The following 2 substituted anilino-4,5,6,7-tetrahydrobenzothiazoles were made using the same process as in Example 70:

Product Subst. Phenylthiourea N u q XNHONH3 l-Ohlorocy- XNHO Ex. No. clohexanone,

parts by wt.

Parts Parts M.P., Crystalli- X by wt. by wt. C. zation Solvent 71 20.2 13.0 10 188189 Ethanol.

72 16.7 13.0 6 184 Isopropanol.

73 16.8 13.2 8 164-165 Benzene.

dispersion of 13.6 parts of N-phenyl-p-phenylene-dithio- BIPHENYLENE-BIS-(2-AMINO-4-SUBSTITUTED urea in 77 parts of methyl Cellosolve at 28 over a period THIAZOLES) of 10 minutes. The reaction mixture is heated at 80 for 3 /2 hours and diluted with 100 parts of 5% sodium bicarbonate. The reaction mixture is extracted with 4 por- Example 74.N,N-p-bipheny[ene-bis-(2-amin0-4-ttions each of 80 parts by volume of ether, the combined ether extracts being washed with Water and dried over anhydrous sodium sulfate. The ether is then distilled off and the residue (23 parts) is freed of a small amount of a soluble contaminant by extraction with hot hexane. The hexane-insoluble fraction (19 parts) is recrystallized from a solvent mixture of isopropanol and benzene. The N,N- bis (4 p t butylphenyl 2 thiazolyl) N phenylp-phenylenediamine, so obtained, melts at 219-220".

2-ARYLAMINO-TETRAHYDROBENZOTHIAZQLES Example 70.2-0-hydr0xyanilino-4,5,6,7-tetrahydrobenzothiazole 2-chlorocyclohexanone (13 parts) and o-hydroxyphenylthiourea (16.8 parts) are dispersed in 150 parts by butylthiazole) 1-br0mo-3,3-dimethylbutanone-2 (14.3 parts) is dissolved in 26 parts by volume of benzene and added drop- Wise over a period of 10 minutes at 27 to a dispersion of p-biphenylene-bis-(Z-thiourea) (12.8 parts) in 127 parts by volume of methyl Cellosolve. The reaction mixture is heated at for 4 hours and then diluted with 300 parts by volume of water, containing 10 parts of sodium bicarbonate, and Well agitated. The mixture is extracted with ether, the ether extract being Washed with water and dried over anhydrous sodium sulfate. The ether is distilled ofi? and the N,N'-p-biphenylene-bis-(2-amin0- 4-t-butylthiazole) (16 parts) is crystallized from a mixture of benzene and chloroform; it melts at 243-244".

218 and 2000 pounds per square inch pressure.

Polyprbpylene+ stabilizer 2 25 Examples 75-77 In a similar fashion to Example 74, other N,N'-p-biphenylene bis (2 amino-4-substituted thiazoles) were made as follows:

Unstabilized polypropylene powder (Hercules Profax 6501) is thoroughly blended with 0.5% by weight of 2,2- imino-bis-4-(p-t-butylphenyl)-thiazole made according to Example 32. The blended material is then milled on a two roller mill at 182 for minutes, after which time the stabilized polypropylene is sheeted from the mill and allowed to cool.

.The milled polypropylene sheet is then cut into small pieces and pressed for 7 minutes on a hydraulic press at The resultant sheet of mil thickness is then tested for resistance to accelerated aging in a forced draft oven at 149. As evident from the table below, the composition of 0.5% by weight of 2,2-imino-bis-4-(p-t-butylphenyl)- I thiazole and polypropylene is stabilized against deteriora- Hours Pol r0 lene alone 3 YD Pl! 500 Grazing is the surface embrittlement (fine cracls on surface) which is an indication of oxidative deterloration.

Other substituted thiazoles which are also efiective at 0.5 by weight in polypropylene are:

2,2-imino-bis-(4-hendecylthiazole) (Ex. 33).

2-(N=phenyl-p-hydroxyphenylamino)-4-phenylthiazole 2-(u-naphthylamino)-4-n-hendecylthiazole (Ex. 59).

2-( u-naphthylamino -4-(p-t-butylphenyl -thiazole (Ex.

N,N'-bis- 4-p-t-butylphenyl-2-thiazolyl) -N-phenyl-pphenylenediamine (Ex. 69).

2- N-l auroyl-Z-hydroxy-S t-octylphenyl amino -4-phenylthiazole (Ex. 17).

In like manner, if either Z-(m-aminoanilino)-4-t-butylthiazole (Ex. 52) or Z-(m-aminoanilino)-4-phenylthiazole Product NH NH I I RC-N 0:5 0:8 II II H II Ex. I v HO CNH -NHC CH N0. NH: N H2 a'Haloketone, Parts by wt. \S/

S Parts by Wt.

R Parts by Wt. M.P., C. Crystallization Solvent I 75".-- 12.8 -C 0 01120]. 15 276-278 Pyridine-benzene.

IT-C12 25 l- 12 215 76 l 6.5 15 258-263 Tetrahydrofuranbenzene.

I C O C H2 01 i 77-4.-- 6. 5 CHa(CH2)1nCHaBr n-CnHza 12 149-151 chloroform.

Example 78 35 according to Example 78, are incorporated into high impact polystyrene (Foster Grant Tufiex, X11516) by milling at 155 in an amount of 0.1% by weight, then the resultant compositions are stabilized against deterioration.

Example 79 A stabilized mineral oil composition is prepared by incorporating into a refined parafiin-type mineral oil of 183 S.U.S. at F. (Regal Oil B, Texas Company) 0.05% by weight of the stabilizer 2-(p-aminoanilino)-4-tbutylthiazole (Ex. 41). The stability of this composition is tested by incorporating therein 20 parts per million of soluble copper as the naphthenate and placing the resultant mixture in a modified Sligh oxidation flask equipped with a mercury manometer (Davis et al., Ind. Eng. Chem., 33 339, March 1941). The flask is maintained in a constant temperature oil bath at The length of time for a pressure drop of 60 mm. from the maximum pressure noted is taken as the time of failure. The stabilized mineral oil does not fail after 96 hours, the blank failing after only 3 /2 hours.

Under the foregoing conditions of Example 79, mineral oil is effectively stabilized also by each of the following compounds:

Z-(p-aminoanilino)-4-phenylthiazole (Ex. 4)

2-(rn-aminoanilino)-4-phenylthiazole (Ex. 6).

2-(p-aminoanilino)-4-n-hendecylthiazole (Ex. 55).

N,N'-o-phenylene-bis-(2-amino-4-methylthiazole) (Ex.

Example 80 Stabilized gasoline is prepared by incorporating into gasoline, having no additives and no stabilizers therein, 0.05 by Weight of 2-(p-aminoanilino)-4-t-butylthiazole (Ex. 41). The gasoline, with and without stabilizer, is tested by the oxygen bomb induction period method (ASTM D525-55), with the result that the gasoline with stabilizer has not failed after 500 minutes, while the blank fails after 250 minutes.

Example 81 Stabilized lard is prepared by incorporating in lard (Tobin Packing Co.) 0.01% by weight of 2-(p-aminoanilino)-4-t-butylthiazole (Ex. 41). The lard, with and without stabilizer, is tested by the oxygen induction period method (ASTM D525-55) with the following modifications: 15 parts of lard sample are tested; the end point is defined as the mid-point of the first hour, in which a pressure drop of 2 lbs. per square inch or greater is noted, followed by an equivalent or greater drop in the succeeding hour. The stabilized lard does not fail after 500 minutes, while the unstabilized lard fails after 108 minutes.

Lard is also stabilized with each of the following antioxidants:

2(o-aminoanilino)-4 (n-dodcylphenyl)-thiazole (Ex.

29) 2-(p-aminoanilino)-4-methylthiazole (Ex. 36)

If cotton seed oil (refined, Welch, Hol-me and Clark) is substituted for lard in the foregoing test and as stabilizer 2-(o-aminoanilino)-4 (n-dodecylphenyl)-thiazole (Ex. 29) is used, then the cotton seed oil containing stabilizer does not fail after 500 minutes, while the unstabilized cotton seed oil fails after 282 minutes.

Example 82 High temperature lubricant (diisoamyladipate) is stabilized by incorporatin therein 2% by weight of 2-(p-aminoanilino)-4-t-butylthiazole (Ex. 41) into said lubricant. The resultant stabilized lubricant composition is compared with the unstabilized lubricant by heating at 175 in presence of air and metallic catalysts according to the test methods described in Military Specification Mil-L-7808c. After 72 hours the blank contains 83% sludge and has increased significantly in acidity. The stabilized lubricant, however, contains less than 15% of sludge and shows no increase in acidity.

Example 83 Heptaldehyde is stabilized by incorporating into the :freshly distilled aldehyde 0.01% by weight of 2,2'-iminobis-(4-t-butylphenyl)-thiazole (EX. 32). The stabilized heptaldehyde is shaken in an oxygen atmosphere in the dark under normal pressure at room temperature (23). The time necessary for absorption of 30 parts by volume of oxygen in 25 parts of heptaldehyde is 89 hours for the stabilized heptaldehyde, but only A hour for heptaldehyde alone.

Heptaldehyde is also effectively stabilized by each of the following compounds:

Z-(m-aminoanilino)-4-t-butylthiazole (Ex. 52) 2-(o-aminoanilino)-tetrahydrobenzothiazole (Ex. 72)

Example 84 Cyclohexene, freshly distilled, is stabilized by addition thereto of 0.001% by weight of the stabilizer 2-(p-aminoanilino)-4-t-butylthiazole (Ex. 41). The effectiveness of this antioxidant in cyclohexene is tested by the ASTM D525-55 oxidation test with the modification that only parts by volume of cyclohexene are used in each bomb. The stabilized cyclohexene runs more than 200 minutes without failure, While unstabilized cyclohexene fails after 30 minutes.

Cyclohexene is also stabilized by each of the following compounds:

2-(o-hydroxyanilino)-4-t-tbutylthiazole (Ex. 42) 2-(p-hydroxyanilino)-4-t-butylthiazole (Ex. 43) 2-(2-hydroxy-5-t-octylanilino)-4-t-butylthiazole (Ex. 48) 2-(o-arninoanilino)-tetrahydrobenzothiazole (Ex. 72)

In like manner to cyclohexene, tetralin is stabilized with 0.001% by weight of each of the following compounds:

2-(p-aminoanilino)-4-phenylthiazole (Ex. 4) 2-(p-hydroxyanilino) 4-p-n-dodecylphenylthiazole (Ex.

Example Paratfin Wax (M.P. 128) is stabilized by incorporating therein 0.001% by weight of 2-(p-aminoanilino)- 4-t-butylthiazole (Ex. 41). The effective stabiliaztion is illustrated by the following odor test: The stabilized paraffin is heated at 121 in the presence of air. A like amount of unstabilized paraffin wax is also heated under the same conditions. After 18 hours, there is no perceptible odor for the stabilized wax. The unstabilized wax, however, exhibits a distinct odor.

Parafiin wax is also stabilized by 0.001% by weight of each of the following compounds:

Z-(p-aminOanilino)-4-rnethylthiazole (Ex. 36) 2-(o-hydroxyanilino) 4-p-n-dodecylphenylthiazole (Ex.

Example 86 Stabilized rubber is prepared by mixing in the cold:

Parts Hevea latex crepe 100.0 Stearic acid 1.5 Zinc oxide 1.0 Diphenylguanidine 1.0 Sulfur 2.5 Z-(p-hydroxyanilino)-4-t-butylthiazole (Ex. 43) 1.0

The resultant mixture is vulcanized at and tested according to ASTM D-120653T. The time required to elongate a test strip from 120 mm. to mm. is 8% hours for the unstabilized rubber, and more than 35 hours for the stabilized rubber. In a similar way poly-isoprene rubber and styrenebutadiene rubber are stabilized.

The rubber of Example 86 is stabilized in like manner, if 1.0 part of one of the following compounds:

2-(o-hydroxyanilino)-4-t-butylthiazole (Ex. 42); or 2-(p-hydroxyanilino) 4 (p-n-dodecylphenyl)-thiazole (Ex. 27); or Z-(p-aminoanilino)-4-phenylthiazole (Ex. 4)

is substituted for 1.0 part of 2- (p-hydroxyanilino -4-t-butylthiazole (Ex. 43

It is understood that in the foregoing Examples 78-86 inclusive, compositions which comprise the oxidizable material of each of said examples therein, are stabilized by effective amounts of the new compounds, prepared according to the preceding Examples177 inclusive.

What is claimed is:

1. A compound of the formula:

No references cited.

ALEX MAZEL, Primary Examiner.

RICHARD J. GALLAGHER, Assisrant Examiner. 

1. A COMPOUND OF THE FORMULA: 